Vat dyestuff of the anthraquinone acridone series



' I havefound;that wvhemworking in thex same ;-:or a similar mannerbut in the:presence ofialphavaminoanthraquinone compound, which mayabe sub'stitutedin the -nucleu's by acarbocyclic aroyl- I amino 'OIT alkoxy group. no "splitting off of halogenatoms but a qcondensation reaction between the :halogenated:anthraquinoneeacridone ancLthe ixaminoanthraquinone:occurs. 1

Iii 35 Patented Mar. 12, 1935 VAT DYESTUFF OF THE ANTHRA'QUINQNE ACRIDONE SERIES Robert Berliner, Leverkusen, near Cologne-onthe-Rhine, Germany, assignor to-Genei'al Ani- -lin"Works inc., New York, N. Y., 'a corporation of Delaware A No -Drawing. Application May 1, 1929, Serial' No.

' "'359,724. In Germany May 8, 19,28

The present invention relates to a process of tageous to add to the reaction mixture a small manufacturing vat dyestuifs'of the anthraquinone amount of copper-pr a suitable copper salt, such series and to the new pro'ductsobtainable thereby. as copper chloride, icopper bromide cuprous bro- It is known that halogenated,anthraquinone- .mide, copper acetate and the like in order to acacridones, containing? or more halogenatoms celerate the reaction. in the molecule, will split off halogenatoms when My new compounds, thus obtainable, are treated with organic or inorganic bases or salts formed according 'to the following equation: of weak acids in the presence of copper or copper compounds (see for example GermanPatent No.

4 Claims.

I prefer to performzthereactionaby starting with a halogenated anthraquinone-acridone of the formula v p rifIwhelin ihl-htwd Xsi stand for halogenatoms and Afi-means'; the anthraquinone nucleus attachedto batheenitr'ogen"atomsin alpha-position; which nuacleus may-besubstituted-bya carbocyclic aroyl aminoor alkoxy group. :Theyformdarkscolored crystalline powders, nearly insoluble in the usual organic solvents, -soluble in strong sulfuric acid, with yellow to brown colorations, and they dye cotton from an alkaline hydrosulfite vat strong dark 0 shades of good fastness properties;

'The following examples illustrate my invention, without limiting it thereto:--- 7 I 7 Example 1.10'\parts by, weight of trichloro wherein the three- Xs stand-for halogenatoms anthraquinone acridonefof the formula "$335 more particularly for brdmo-z or chloroatoms, obtainable for instance by brominating or chlorinating the corresponding: anthra'quinoneacridone according to known methods, and reacting upon this starting material with the alpha-aminoanthraquinone, in the presence of a suitable high 0 boiling organic solvent and an acid bindingmen dium at. temperatures between: about 180 0.1mm

j'the boiling point'of the reaction mixture. Assuit- 45 able high boiling organic solvents nitrobenzene, "naphthalene, trichlorobenzene or the'like maybe vo mentioned by way vof example, Whereas as acid '5 I "binding media sodium'acetat'e, potassium-carbonate;-sodium carbonate and the-like'w'ill be obtainable, for'example in accordance with the suitable ones. some'cases it-wi1l beadvan- -GermanPatent No.258,561,Example 4, are"heated to boiling for some hours in 100 parts by weight of naphthalene with 8 parts by weight of 1- benzoylamino-5-aminoanthraquinone and 2.5 parts by weight of sodium acetate with the addition of 0.2 part by weight of cupric chloride until there is no further increase in the quantity of the condensation product, which separates in small greyish green needles. The melt is worked up in the customary manner, if desired or necessary with the addition of a diluent. The greyish green crystalline powder obtained dissolves in concentrated sulfuric acid with a yellowish brown coloration. The product dyes cotton from an alkaline hydrosulfite vat strong gray shades of good fastness properties. It corresponds to the formula:

| HsCu-OC.NH 1) sponds to the formula:

:001 HN i O NH.CO.CeHu

Example 3.- parts by weight of trichloroanthraquinone acridone as used in Example 1 are heated to boiling for some hours in 100 parts by weight of naphthalene with 3 parts by weight of a-aminoanthraquinone, 2 parts by weight of soium acetate and 0.1 part by weight of cupric chloride. The condensation product separates in the form of dark crystals, which dissolve in concentrated sulfuric acid with a yellowish brown coloration. The product, which dyes cotton from an alkaline hydrosulfite vat greyish shades, corresponds tothe formula:

EN 0 (ll; 00

NH 0 ll Example 4.20 parts by weight of the trichloroanthraquinone acridone of Example 1, 12 parts by weight of 1-amino-4-methoxy anthraquinone, 200 parts by weight of naphthalene, 5 parts by weight of sodium acetate and 0.5 part by weight of cupric chloride are heated to boiling until there is no further increase in the quantity of the condensation product, which separates in form of a dark crystal powder. The new compound, which corresponds to the formula:

dissolves in concentrated sulfuric acid with a blueish green coloration. On pouring into water corinth colored flakes are obtained. The product dyes cotton from an alkaline hydrosulfitevat strong corinth shades.

In the followingclaims the term copper catalyst is intended to comprise copper and copper compounds, particularly its salts.

I claim:- 1. As a new compound, the vat dyestuff of the formula:

I HsCr-O C-NH said compound being a greyish green crystalline powder, dissolving in concentrated sulfuric acid with a yellowish brown coloration, and dyeing cotton from an alkaline hydrosulfite vat strong gray shades of good fastness properties.

2. As a new compound, the vat dyestuff of the formula:

said compound being a dark crystalline powder,

dissolving in strong sulfuric acid with a yellowish olive coloration, and dyeing cotton from an alkaline hydrosulfite vat strong grey shades.

3. The product of the general formula.v

i O \N Ag E NH wherein either X or X1 is benzoyl amino, the other being hydrogen, said products being dark, crystalline powders nearly insoluble in the usual organic solvents, soluble in strong sulfuric acid,

with yellow to brown colorations, dyeing cotton I from an alkaline hydrosulfite vat strong dark shades of good fastness properties.

ROBERT BERLINQR. [L. s.] 

